Monoazo-pigments



United States Patent 3,331,832 MONOAZO-PIGMENTS Hansrolf Loefiel, Neuallschwil, Switzerland, assignor to Ciba Limited, Basel, Switzerland, a Swiss company No Drawing. Filed Oct. 18, 1963, Ser. No. 317,140 5 Claims priority, application Switzerland, Oct. 23, 1962, 12,403/62; Sept. 17, 1963, 11,463/63 7 Claims. (Cl. 260-192) The present invention provides valuable new monoazo 10 pigments of the general formula (1) N=NR1 in ('3 ON HR in which R represents the grouping R3C ONHR4NHOOR5 R represents an anthraquinone radical, R R and R represents aromatic radicals, especially benzene radicals, and R represents the radical of a coupling component that contains a hydroxyl group or an enolizable keto group in ortho-position to the azo group. Of special interest are dyestuffs of the formula in which X represents a halogen atom or a trifluoromethyl group, Y represents hydrogen or halogen atoms, X X Y Y Z and Z represent hydrogen or alkyl or alkoxy groups or especially halogen atoms.

The new dyestuffs can be obtained for example When (a) a monocarboxylic acid halide free from acidic groups imparting solubility in water that corresponds to the formula I 2 C OHal is condensed in a molar ratio of 1:1 with an amine of the formula (4) H NR CONHR NHCOR or (b) a monocarboxylic acid halide free from acidic groups imparting solubility in Water that corresponds to the formula I =NR1 1132 0 ONHR3-'C ()Hal is condensed in a molar ratio of 1:1 With an amine of the formula 3,331,832 Patented July 18, 1967 in which formulae the radicals R and R have the meanings given above.

The azo carboxylic acids from which the acid halides of Formula 3 are :derived are advantageously obtained by coupling a diazotized aminoanthraquinone, for eXample, an aor fl-aminoanthraquinone with a phenolic o1 enolic coupling component that contains a carboxylic acid group or a carboxylic acid ester group; in the latter case, hydrolysis of the ester group is necessary. The following aminoanthraquinones may be mentioned:

l Z4 a 1-amino-3-cyanoanthraquinone, 1-amino-4-nitroanthraquinone, 1-amino-2-bromo-4-cyanoanthraquinone, Z-aminoanthraquinone,

2-amino-3 -chloranthraquinone, 2-amino-3 -bromant-hraquinone, 2-amino-1 3-dichloranthraquinone, 2-amino-3-methoxyanthraquinone, and S-amino-l :9-isothiazole-anthrone.

As coupling components 2-hydroXy-3-naphthoic acid, 6-bromo-2-hydroxy-3-naphthoic acid and 6-methoxy-2- hydroxy-S-napthoic acid are mainly used. The following may also be mentioned: 2-hydroXycarbaZole-3-carboxylic acid, 2-hydroxydiphenyleneoxide-3-carboxylic acid, 2-hydroxyanthracene-3-carb0xylic acid, l-(metaor para-carboxyphenyl)-3-methyl-5-pyrazolone,

aceto-acetic acid ethyl ester, and 3- or 4-acetoacetylaminobenzene carboxylic acid.

The azocarboxylic acids thus obtained are treated With agents that are capable of converting carboxylic acids into their acid halides, for example, their acid chlorides or bromides, particularly such agents as phosphoric acid halides, for example, phosphorus pentabromide or phosphorus trichloride or phosphorus pentachloride, phosphorus oxyhalides and advantageously thionyl chloride.

Treatment with such acid halogenating agent is advantageously carried out in an inert organic solvent such as dimethylformarnide or .a chlorobenzene, for example, monochlorobenzene, dichlorobenzene, toluene, xylene or nitrobenzene; dimethylformamide may also be added when the five last-mentioned solvents are used.

In the preparation of the carboxylic acid halides it is generally of advantage first of all to dry the azo com-.

pounds which have been prepared in aqueous medium, or

to free them from water by azeotropic distillation in an organic solvent. If desired, this azeotropic drying can be carried out immediately prior to the treatment with the acid halogenating agents.

, In method (a) of the present process the monocarboXylic acid halides so obtained are condensed in a molar ratio of 1:1 with aromatic monamines of the Formula 4. As examples the following amines may. be mentioned:

2:5 -dichloro-1 -benzoylamino-4(4'-chloro-3-amino) benzoylaminobenzene,

2:5-dichloro-1-benzoylamino-4 (2:4'-dichloro-5 amino) -benzoylaminob enzene,

2:5 dichloro-1-benzoylamino-4 3-an1ino benzoylaminobenzene,

2:5 -dichloro- 1-benzoylarnino-4 (4'-methoxy-3-amino benzoylaminobenzene,

2:S-dimethyl-1-benzoylamino-4(3-amino) benzoylaminobenzene, 7

2:5 -dimethyl-1 -benzoylamino-4 (4'-chloro-3 '-amino) V benzoylamin ob enzene,

2:5 dimethyl- 1-benzoylamino-4(4'-methoxy-3 '-amino benzoylaminobenzene,

V 2-chloro-5-methoxy-1-benzoylamino-4(4'-rnethoxy-3'- amino -benzoylaminobenzene,

' 2-chloro-5-methoxy-l-benzoylamino-4(4' chloro-3'-.

amino) -benzoylarninobenzene, 2-methyl-5-chloro-1-benzoylamino-4 (4'-methoxy-3 amino) -benzoylaminobenzene, 2-methyl-5-chloro-1-benzoylamino-4(4-chloro-3 amino) -benzoylaminobenzene, 2-chloro-5-methoxy-1-benzoylamino-4( 3'-amino) benzoylaminobenzene,

V 2-methyl-5-chloro-l-benzoylamino-4( 3 '-amino 7 benzoylaminobenzene, 2:S-dimethyl-l-benzoylamino-4(2':4-dichloro-5'- amino) -benzoylaminobenzene, 2:5 -dichloro-1 (4-chloro) -benzoylaminobenzene-4(4"- chloro-3"-amino -benzoylaminobenzene,

' 2:5-dichloro-l (4'-chloro -benzoylamino-4(2":4"-

dichloro- "-amino) -benzoylaminob enzene, 2'z5-dichloro-1(4 chloro)-benzoylamino-4(4-chloro 3 "-amino) -benzoylaminob enzene, 2:5'-'dichloro-1(2:4'-dichloro)-benzoylamino-4(2:4-

dichloro-5 -amino) -benzoyl aminob enzene, 2:5 -dichloro-1 :wnaphthoylamino-4 (2':4-dichloro-5 amino) -benzoylaminobenzene, 2:5 -dichloro-1 (2:4-dichloro -benzoylamino -4( 3"- amino) -benzoyl aminob enzene, 2 arnin'o-terephthalic acid dianilide,

JZ-aminO-terephthalic acid-di-(para-chloranilide) and Z-amifio-terephthalic acid-di-(meta-trifluoromethylanilide) The condensation between the carboxylic acid halides of the kind defined above and the amines is advantageously carried out in. an anhydrous medium. Under these conditions it generally proceeds surprisingly easily at temperatures within the boiling range of the common organic solvents such as toluene, monochlorobenzene, dichlorobenzene, trichlorobenzene, nitrobenzene and the like. In order to accelerate the reaction it is generally of advantage to mean agent capable of binding acid, for example, anhydrous sodium acetate or pyridine. Some of the dyestuffs obtained are crystalline and some are amorphous and they are generally obtained in a good yield and in a pure state. It is generally of advantage first to separate the acid chlorides prepared from the carboxylic tion of colored lacquers or as lake-formers; and for coloring solutions and products made from cellulose acetate, nitrocellulose, natural or synthetic resins such as polymerization or condensation resins, for example, aminoplasts, alkyd resins, phenoplasts, polyolefines such as polystyrene, polyvinyl chloride, polyethylene, polypropylene, polyacrylonitrile, rubber, casein, silicone and silicone resins. They can also be used with advantage in the manufacture of colored pencils, cosmetic preparations and laminated sheet material. 7

In contrast with comparable dyestuits described in United States specification No. 2,273,116, patented February 17, 1942, to Georg Kraenzlein et al., the dyestuffs.

obtained by the process of the invention are distinguished by a substantially better fastness to migration.

The following examples illustrate the invention; Unless otherwise stated, the parts'and percentages are by weight.

Example 1 I 130 parts of sulfuric acid monohydrate were cooled to 10 C. and 7.1 parts of sodium nitrite were added in small portions with rapid stirring. The nitrosyl sulfuric acid was heated to 70 C. in the course of40 minutes, kept at that temperature for 30 minutes and then cooled to room temperature. 25.75 parts of 1-amino-3-chloranthraquinone were next added in the course of 1 hour,

and the mixture stirred for a further hour. The sulfuric acid solution was cautiously poured on to' 350 parts of ice, the diazonium sulfate being precipitatedin the form of a yellow suspension.

The solution of the coupling component was prepared as follows: 19.1 parts of 2:3-hydroxynaphthoic acid were dissolved in 400 parts of a 1:1 alcohol and water mix-,

ture and 20 parts of 30% aqueous sodium hydroxide. solution. After filtering until clear, 30 parts of sodium acetate were added and the pH value adjusted to 6 with acetic acid.

The solution thus prepared was cooled to 10 C. and I the diazonium sulfate obtained as described in the first.

paragraph above was run in, concentrated sodium'hydroxide solution being simultaneously added dropwise (pH value 4 to 6). After the coupling the reaction mixture was heated to 70 C., filtered, and the filter residue washed until free from salt.,190 parts of moist filter residue were obtained.

The press-eake was 'freed from water aieotropically V by heating to 150 C; internal temperature in 650 parts of ortho-dichlorobenzene (with use of a descending condenser). After cooling to C., one part of dimethyl formamide and 24 parts of thionyl chloride were added dropwise and the whole stirred for a further two hours at to C. The reaction mixture was cooled to 20 C., filtered, the filter residue washed with 52O parts of dichlorobenzene and 400 parts of benzene, and the 3 acid chloride dried in vacuov at 50C.; yield: 43.35 parts.

2.375 parts of the acid chloride were introduced at room temperature into 170 partsof dichlorobenzene. 2.46 parts of 2:5-dichloro-LbenZoyLaminoA-(Z:4-dichloro-5'-amino)-benzoylaminobenzene, dissolved in .80 a parts of hot dichlorobenzene, were then added. The, whole was heated to60 C., the temperature wasraised to C. in the course of 8 hours, and stirring continued for a further 8 hours at 140 C(The pigment obtained was filtered oif at l00 C. and then washed with 250 parts of hot dichlorobenzene, 120 parts of methanol and,

parts of water 3.85 parts of a dyestufl of the formula.

1-amino-2-methyl-4-bromanthraquinone was converted into 1 bromo 3 methylanthraquinone (M.P. 204 to 205.5 C.) by diazotizing and then boiling the diazonium salt in alcohol. 1-chloro-3-trichloromethylanthraquinone (M.P. 155.5 to 156.5 C.) was obtained by chlorination in boiling ortho-dichlorobenzene. Treatment with anhydrous hydrofluoric acid yielded 1-chloro-3-trifiuor'omethylanthraquinone, which gave l-toluene-sulfonyl-amino- 3-trifiuoromethylanthraquinone (M.P. 228.5 to 229 C.) when reacted with para-toluene sulfonamide. The 1- toluene-sulfonylamino 3 trifiuoromethylanthraquinone was hydrolysed with cold, concentrated sulfuric acid form 1 amino 3 trifiuoromethylanthraquinone (M.P. 223.5 to 224.5 C.)

Analysis-Calculated: C, 61.86; H, 2.77; N, 4.81; F, 19.57. Found: C, 62.01; H, 2.90; N, 4.71; F, 19.60.

Example 2 13.38 parts of 1-amino-3-chloranthraquinone were diazotized with 75 parts of monohydrate and 4 parts of sodium nitritein a mannner analogous to that described in Example 1, and the reaction mixture poured on to 250 parts 'of ice.

10.92 parts of 100% 1-(3'-carboxy)-phenyl-3-methyl- 5-pyrazolone were dissolved in 260 parts of a 1:1 alcohol and water mixture and parts of 30% sodium hydroxide solution. After filtering until clear, 20 parts of sodium acetate were added and the pH value adjusted to 6 with acetic acid. 7

Coupling was carried out at 1 to 10 C. at a pH value of 4-6 in a manner analogous to that described in Example 1. 70 parts of a brown filter residue were obtained.

The press-cake was dried azeotropically in 390 parts of dichlorobenzene in a manner analogous to that described in Example 1. After cooling to 95 C., one part of dimethylformamide, 12 parts of thionyl chloride and a further 130 parts of dichlorobenzene were added dropwise. Stirring was continued for 2 hours at 100 C., the reaction mixture cooled to 20 C., filtered, and the filter residue washed with 340 parts of dichlorobenzene and 300 parts of benzene. After drying, 17.5 parts of light brown acid chloride were obtained.

2.55 parts of the acid chloride were introduced into 130 parts of dichlorobenzene and then condensed with 2.60 parts of 2 S-dichloro-1-benzoy1amino-4-(2' :4'-dichlor0-5'- amino)-benzoylaminobenzene, dissolved in 100 parts of hot dichlorobenzene, in a manner analogous to that de scribed in Example 1. The reaction mixture was filtered, the residue washed with 160 parts of hot dichlorobenzene, 80 parts of methanol and 100 parts of Water; yield: 3.9 parts of a yellow dyestuff of the formula 8 Example 3 51.5 parts of l-amino-3-chloranthraquinone were diazotized with 300 parts of monohydrate and 16 parts of sodium nitrite in a manner analogous to that described in Example 1 and the diazo solution was poured on to 1000 parts of ice.

Meanwhile 26 parts of acetoacetic acid ester were dissolved in 200 parts of isopropanol, 200 parts of water and 28 parts of 30% aqueous sodium hydroxide solution, a

further 600 parts of water were added, the pH value was 'free from salt. After drying, 77.5 parts of a yellow azo ester melting at 186 to 189 C. were obtained of the formula fi ITEN-CH-C 0 0 02m 69 parts of this ester, 625 parts of methanol, 500 parts of water and 78 parts of aqueous 30% sodium hydroxide solution were heated to to 58 C. for minutes. The reddish brown suspension was acidified, the yellow acid that precipitated was filtered off and washed until the washings ran neutral. After drying, 63.9 parts of an-azo acid melting at 248 to 250 C. were obtained.

698 parts of the azo acid were heated in 700 parts of dichlorobenzene to C., and then 0.5 part of dimethylformamide and 59 parts of thionyl chloride were added.

The reaction mixture went into almost complete solution after 30 to 40 minutes. After stirring at to C. for a period totalling 1 /2 hours, the solution was cooled to 0 C., filtered, and the filter residue washed with parts of dichlorobenzene and 300 parts of .benzene. 45.8 parts of a dry acid chloride melting at 228 to 236 C. (with decomposition) were obtained.

195 parts of this acid chloride were suspended in 130 parts of dichlorobenzene. 2.28 parts of-'2:5-dichloro-l benzoylamino-4-(4'-chlor0-3'-amino) benzoylaminobenzene dissolved in 190 parts of dichlorobenzene were then added. The whole was stirred for 2 /2 hours at 100 C., the temperature raised to C. in the course of 4 hours,

It colored polyvinyl chloride yellow tints possessing a ,good fastness to light and to migration.

By using 2-chloro-5-methoxy-1-benzoylamino-4-(2':4- dichloro-5-amino)-benzoylaminobenzene as condensation and the mixture was then allowed to react for 10 hours at 140 to C. The reaction mixture was filtered at 90 C., the residue washed with 390 parts of dichlorobenzene, 200 parts of methanol and 200 parts of water; yield: 3.5

base, a dyestulf possessing similar properties was obtained. ,7 parts of a greenish yellow pigment of the formula 01 300113 lTI=NOH-CONH I 01 CONH NH 06 I o which gave greenish yellow tints possessing a good fastness to migration when worked into polyvinyl chloride on a roller mill.

Example 4 5.15 parts of 1-amino-3-chloranthraquinone were diazotized with 50 parts of monohydrate and 1.5 parts of sodium nitrite in a manner analogous to that described in Example 1, and the solution poured on to 15 0 parts of ice. 6.81 parts of 2:3-hydroxynaphthoic acid-2':4'-dichloro- 5'-carboxylic acid anilide were dissolved in 150 parts of a 1:1 isopropanol and water mixture and 4 parts of 30% sodium hydroxide solution. After filtering until clear, parts of sodium acetate were added and the pH Value adjusted to 6 with acetic acid.

Coupling was carried out at 10 C. and at a pH value of 4 to 6 in a manner analogous to that described in Example 1. 50 parts of red filter residue were obtained.

The press-cake was dried azeotropically in 195 parts of dichlorobenzene in a manner analogous to that described in Example 1. After cooling to 95 C., 1.2 parts of dimethylformamide and 6.5 parts of thionyl chloride were added dropwise. The whole was stirred for 2 hours at 100 C., cooled to 20 C., filtered, and the filter residue washed with 120 parts of dichlorobenzene. and 120 parts a in which A is anthraquinonyl chloroanthraquinonyl, or trifluoromethyl anthraquinonyl, Y a member selected from the group consisting of hydrogen, chlorine, bromine and lower alkoxy, X X Y Y Z and Z represent members selected from the group consisting of hydrogen, chlorine, bromine, lower alkyl and lower alkoxy.

2. A mon'oazo pigment of the formula I C O N H- in which X is a member selected from the group consisting of chlorine, bromine and trifluoromethyl, Y a member selected from the group consisting of hydrogen, chlorine,

bromine and lower alkoxy, X X Y Y Z and 2.;

represent members selected from the group consisting of hydrogen chlorine, bromine, lower alkyl and lower alkoxy.

3. A monoazo pigment of the formula Halogen of benzene. After drying, 10.05 parts of a red acid chloride were obtained.

1.50 parts of this acid chloride were introduced into parts of dichlorobenzene and then condensed as described with 0.668 part of 2:5-dichloro-4-benzoylaminoin which Y a member selected from the group consisting of hydrogen, chlorine, bromine and lower alkoxy, X X Y Y Z and Z represent members selected from the group consisting of hydrogen, chlorine, bromine, lower 7 5 alkyl and lower alkoxy.

, 4. A dyestuff of the formula N=N o ONHQCI n II V I o 5. The dyestufi of the formula O N:N G O NH 6. The dyestufi of the formula 7. The dyestutf of the formula V 7 OH 01 I l 1\|I==N- -00NHQ01 11 CONHQNHOO-O -OF3 V V 01 No references cited.

CHARLES B. PARKER, Primary Examiner. DONALD PAPUGA, Assistant Examiner,

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,331 ,832 July 18 1967 Hansrolf Loeffel It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 10, lines 11 to 21, the right-hand side of the formula should appear as shown below instead of as in the patent:

columns 11 and 12 about lines 15 to 20 the right-hand side of the formula should appear as shown below instead of as in the patent: I

CONH NHCO-O Signed and sealed this 30th day of July 1968.

(SEAL) Attest:

EDWARD J. BRENNER Attesting Officer 

1. A MONOAZO PIGMENT OF THE FORMULA 